TW201918375A - Metal-clad laminate and circuit board of which the insulating resin layer is excellent in dimensional stability even in the high temperature and the high pressure environments, or the environment with varying humidity - Google Patents

Abstract

The present invention provides a metal-clad laminate capable of reducing the dimensional change relative to the changes in temperature, humidity and pressure during the steps such as a circuit processing step, a substrate laminating step, and a component mounting step, and the changes in temperature and humid environment between steps. A metal-clad laminate comprises an insulating resin layer and a metal layer, wherein the insulating resin layer has a non-thermoplastic polyimide layer and a thermoplastic polyimide layer, and satisfies: (i) a value of in-plane birefringence ([Delta]n) is 2×10<SP>-3</SP> or less; (ii) the deviation [[Delta]([Delta]n)] of the in-plane birefringence ([Delta]n) in the width direction (TD direction) is 4×10<SP>-4</SP> or less.

Description

Metal-clad laminated board and circuit substrate

The invention relates to a metal-clad laminated board and a circuit board.

In recent years, with the development of miniaturization, weight reduction, and space saving of electronic equipment, flexible printed wiring boards (FPC: Flexible Printed Circuits) that are thin and light, have flexibility, and have excellent durability even after repeated bending. The need is increasing. FPC can achieve stereo and high-density installation even in a limited space. Therefore, its use is being expanded to hard disk drives (HDD), digital Versatile Disc (DVD), and mobile phones. Wiring of moving parts of electronic equipment, or parts such as cables and connectors.

FPC is manufactured by etching a copper layer of a copper-clad laminate (CCL) and performing wiring processing. In mobile phones or smart phones, for FPCs that are continuously bent or bent 180 °, rolled copper foil is mostly used as the material of the copper layer. For example, Patent Document 1 proposes that the bending resistance of a copper-clad laminated board produced using a rolled copper foil is prescribed by the number of times of crack resistance. In addition, Patent Document 2 proposes a copper-clad laminate using a rolled copper foil that is specified in terms of gloss and number of bends.

During the photolithography step performed on the copper-clad laminated board or the process of installing the FPC, bonding, cutting, exposure, and etching are performed with reference to an alignment mark provided in the copper-clad laminated board. And other processing. The processing accuracy in these steps becomes important in maintaining the reliability of the electronic device equipped with the FPC. However, a copper-clad laminate has a structure in which a copper layer and a resin layer having different thermal expansion coefficients are laminated. Therefore, a stress is generated between the layers due to a difference in the thermal expansion coefficient between the copper layer and the resin layer. A part or all of the stress is relieved when the copper layer is etched for wiring processing, thereby causing expansion and contraction, and it becomes a factor that changes the size of the wiring pattern. Therefore, a dimensional change finally occurs in the stage of the FPC, which causes a poor connection between wirings or between wirings and terminals, thereby reducing the reliability or yield of the circuit board. Therefore, in a copper-clad laminated board as a circuit board material, dimensional stability is a very important characteristic. However, in the patent documents 1 and 2, the dimensional stability of the copper-clad laminate is not considered at all.

In addition, Patent Document 3 proposes that in order to reduce the thermal expansion coefficient of the insulating resin layer and improve the dimensional stability, a flexible metal-clad laminate including a copper foil and a non-thermoplastic polyimide layer is provided without a thermoplastic polyimide layer. As the diamine component of the non-thermoplastic polyfluorene imide layer, p-phenylenediamine (p-PDA) or 2,2'-dimethyl-4,4'-diaminobiphenyl ( 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) diamine compounds and 1,3-bis (4-aminophenoxy) benzene (1,3-bis (4-aminophenoxy) benzene, TPE-R) and other diamine compounds. Although p-PDA is a monomer that lowers the coefficient of thermal expansion and contributes to dimensional stability, it has a problem in that the molecular weight of the p-PDA is increased, and the concentration of the fluorene imine is increased, and the moisture absorption of the polyfluorene is increased. If polyimide has a high hygroscopicity, there is a problem that dimensional change or warpage easily occurs due to environmental changes such as heating during circuit processing.

On the other hand, Patent Document 4 discloses that in a multilayer polyimide film in which crack generation during circuit processing is suppressed, m-TB and p-PDA are used in combination as a raw material of a non-thermoplastic polyimide Diamine compound. However, in the monomer composition of Patent Document 4, the molar ratio of p-PDA in the diamine compound is too large. Therefore, there is a problem similar to that described above: polyimide has a high hygroscopicity, and it is caused by circuit processing. As the environment changes with time, dimensional changes or warpage are likely to occur. In addition, Patent Document 4 describes that m-TB, p-PDA, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane (2,2-bis [4- (4- When aminophenoxy) phenyl] propane (BAPP) is used in combination as a diamine compound, crack resistance is deteriorated. In this case, since the molar ratio of p-PDA in the diamine compound is too large, it is considered that there is a problem that the polyimide has a high hygroscopicity as described above. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2014-15674 (Scope of Patent Application, etc.) [Patent Literature 2] Japanese Patent Laid-Open Publication No. 2014-11451 (Scope of Patent Application, etc.) [Patent Literature 3] Japanese Patent No. 5162379 (Scope of patent application, etc.) [Patent Document 4] WO2016 / 159104 (Synthesis Example 6, Synthesis Example 9, etc.)

[Problems to be Solved by the Invention] An object of the present invention is to provide a method capable of reducing changes in temperature, humidity, and pressure in steps such as a circuit processing step, a substrate lamination step, and a component mounting step, and a change in temperature and humidity environment between steps In terms of dimensional changes, metal-clad laminates. [Means for solving problems]

The present inventors conducted diligent research, and as a result, found that the above-mentioned problem can be solved by controlling the in-plane birefringence (Δn) of the insulating resin layer, and the present invention has been completed.

That is, the metal-clad laminate of the present invention includes: an insulating resin layer; and a metal layer laminated on at least one side of the insulating resin layer. In the metal-clad laminate, the insulating resin layer includes a non-thermoplastic polymer. The non-thermoplastic polyfluorene imide layer of fluorene imine has a thermoplastic polyfluorene imide layer containing a thermoplastic polyfluorene imine on at least one side. Furthermore, the metal-clad laminate of the present invention is characterized in that the insulating resin layer satisfies the following condition (i) and condition (ii), and satisfies the following condition (iii), or condition (iv) and condition (v) Both, or both condition (vi) and condition (vii). The value of the in-plane birefringence (Δn) is 2 × 10 ^-3 or less. The deviation [Δ (Δn)] of the in-plane birefringence (Δn) in the width direction (transverse direction (TD) direction) is 4 × 10 ^-4 or less. The difference (Δnh-Δn) between the value of the in-plane birefringence (Δnh) after heating at 250 ° C. for 30 minutes and the value of the in-plane birefringence (Δn) before heating is ± 2 × 10 ^-4 or less. In the thickness direction of the non-thermoplastic polyimide layer, the birefringence (Δna) at a point of 1.5 μm in the direction of the central portion with one surface as the base point and the direction of the central portion with the other surface as the base point. The difference (Δna-Δnb) in the birefringence (Δnb) at the 1.5 μm point is ± 0.01 or less. The difference between the Δna and the Δnb and the average value (Δnv) of the total (Δna + Δnb + Δnc) of the birefringence (Δnc) in the central portion in the thickness direction is in any of the Δna and Δnb Both are below ± 0.01. After drying at 80 ° C. for 1 hour, the moisture absorption (A _m ) after humidity adjustment for 4 hours at 23 ° C. and 50% relative humidity (Relative Humidity, RH) is 1.0% by weight or less. After drying one hour at 80 deg.] C, constant temperature and humidity at 23 ℃, 50% RH, the moisture transfer rate (A _m1) and after 1 hour a wet moisture absorption in the same conditions for its humidity for 2 hours (A _m2 The difference (A _m2 -A _m1 ) is 0.2% by weight or less.

In the metal-clad laminate of the present invention, the non-thermoplastic polyfluorene imide may include a tetracarboxylic acid residue and a diamine residue, and 100 mol parts of all diamine residues may be represented by the following general formula ( The diamine residue derived from the diamine compound represented by 1) is 20 mol parts or more.

[Chemical 1]

In the general formula (1), the linking group Z represents a single bond or -COO-, and Y independently represents a monovalent hydrocarbon having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom or a phenyl group. Or a perfluoroalkyl group or an alkenyl group having 1 to 3 carbon atoms, n represents an integer of 0 to 2, and p and q independently represent an integer of 0 to 4.

Regarding the metal-clad laminate of the present invention, the diamine compound derived from the diamine compound represented by the general formula (1) with respect to 100 mol parts of all diamine residues contained in the non-thermoplastic polyimide The amine residue may be in the range of 70 mol parts to 95 mol parts, and the total amount of the diamine residue selected from the following general formula (2) and general formula (3) may be 5 mol parts to 30 Morse range.

[Chemical 2]

In the general formula (2) and the general formula (3), R ₅ , R ₆ , R _7, and R ₈ each independently represent a halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms which may be substituted with a halogen atom. , Or alkenyl, X independently represents selected from -O-, -S-, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CO-, -COO-,- Divalent group in SO _2- , -NH- or -NHCO-, X ₁ and X ₂ each independently represent a single bond and are selected from -O-, -S-, -CH _2- , -CH (CH ₃ ) -, -C (CH ₃ ) _2- , -CO-, -COO-, -SO _2- , -NH- or -NHCO-, but both X ₁ and X ₂ are single bond Except in this case, m, n, o, and p independently represent integers of 0 to 4.

In the metal-clad laminate of the present invention, the thermoplastic polyfluorene imide may include a tetracarboxylic acid residue and a diamine residue, and is selected from the general formula (100 mol parts with respect to all diamine residues) The total amount of the diamine residues in 2) and the general formula (3) is 50 mol parts or more.

In the metal-clad laminate of the present invention, the diamine residue represented by the general formula (2) may be a diamine residue derived from 1,3-bis (4-aminophenoxy) benzene. The diamine residue represented by the general formula (3) may be a diamine residue derived from 2,2-bis [4- (4-aminophenoxy) phenyl] propane.

In the metal-clad laminate of the present invention, a thickness ratio (A) / (B) of the thickness (A) of the non-thermoplastic polyimide layer and the thickness (B) of the thermoplastic polyimide layer may be 1 In the range of -20.

In the metal-clad laminate of the present invention, the length in the width direction (TD direction) may be 490 mm or more.

The circuit board of the present invention is obtained by processing the metal layer of the metal-clad laminate according to any one of the above into wiring. [Effect of the invention]

The metal-clad laminate of the present invention satisfies condition (i) and condition (ii), and satisfies condition (iii), or both condition (iv) and condition (v), or both condition (vi) and condition (vii) Therefore, even in a high-temperature, high-pressure environment, or an environment where humidity changes, the dimensional stability of the insulating resin layer is excellent. Therefore, it is difficult to change the environment due to circuit processing steps, substrate lamination steps, and component mounting steps (for example , High temperature or high pressure, humidity changes, etc.) and other adverse conditions such as warping. Especially in a wide metal-clad laminate, the total width of the insulating resin layer also has a low dimensional change rate and stable dimensions. Therefore, the FPC obtained from the metal-clad laminate can be mounted at a high density. Therefore, by using the metal-clad laminated board of the present invention as an FPC material, the reliability and yield of the circuit substrate can be improved.

Next, embodiments of the present invention will be described.

<Metal-clad laminate> The metal-clad laminate according to this embodiment includes an insulating resin layer and a metal layer laminated on at least one surface of the insulating resin layer.

<Insulating resin layer> In the metal-clad laminate of the present embodiment, the insulating resin layer has a thermoplastic polyimide layer on at least one side of the non-thermoplastic polyimide layer. That is, the thermoplastic polyimide layer is provided on one or both sides of the non-thermoplastic polyimide layer. For example, in the metal-clad laminate of the present embodiment, a metal layer is laminated on the surface of the thermoplastic polyimide layer. Here, the so-called non-thermoplastic polyimide is generally a polyimide that does not show adhesiveness even when softened by heating. In the present invention, a dynamic viscoelasticity measuring device (dynamic mechanical analyzer) is used. , DMA)) is a polyimide having a storage elastic coefficient at 30 ° C. of 1.0 × 10 ⁹ Pa or higher and a storage elastic coefficient at 360 ° C. of 1.0 × 10 ⁸ Pa or higher. In addition, the so-called thermoplastic polyimide is generally a polyimide whose glass transition temperature (Tg) can be clearly confirmed. In the present invention, the storage elastic coefficient at 30 ° C measured using DMA is 1.0 × 10 Polyimide having a storage elastic coefficient of ⁹ Pa or more and a temperature of less than 1.0 × 10 ⁸ Pa at 360 ° C.

In the metal-clad laminate according to this embodiment, the insulating resin layer satisfies the following condition (i) and condition (ii), and also satisfies condition (iii), or both condition (iv) and condition (v), or condition (vi ) And condition (vii). The value of the in-plane birefringence (Δn) is 2 × 10 ^-3 or less. The deviation [Δ (Δn)] of the in-plane birefringence (Δn) in the width direction (TD direction) is 4 × 10 ^-4 or less. The difference (Δnh-Δn) between the value of the in-plane birefringence (Δnh) after heating at 250 ° C. for 30 minutes and the value of the in-plane birefringence (Δn) before heating is ± 2 × 10 ^-4 or less. In the thickness direction of the non-thermoplastic polyimide layer, the birefringence (Δna) at a point of 1.5 μm in the direction of the central portion with one surface as the base point and the direction of the central portion with the other surface as the base point. The difference (Δna-Δnb) in the birefringence (Δnb) at the 1.5 μm point is ± 0.01 or less. The difference between the Δna and the Δnb and the average value (Δnv) of the total (Δna + Δnb + Δnc) of the birefringence (Δnc) in the central portion in the thickness direction is in any of the Δna and Δnb Both are below ± 0.01. After drying at 80 ° C. for 1 hour, the moisture absorption (A _m ) after humidity adjustment for 4 hours at 23 ° C. and 50% RH was 1.0% by weight or less. After drying one hour at 80 deg.] C, constant temperature and humidity at 23 ℃, 50% RH, the moisture transfer rate (A _m1) and after 1 hour a wet moisture absorption in the same conditions for its humidity for 2 hours (A _m2 The difference (A _m2 -A _m1 ) is 0.2% by weight or less.

Regarding the condition (i), when the value of the in-plane birefringence (Δn) exceeds 2 × 10 ^-3 , the anisotropy of the in-plane orientation becomes large, and this causes the deterioration of dimensional stability. Although the lower limit of the value of Δn is not particularly limited, the orientation from the in-plane orientation is isotropic and the dimensional stability is improved. On the other hand, the warpage caused by the excessive decrease in the thermal expansion coefficient and mismatch with the thermal expansion coefficient of the metal foil is suppressed. From a viewpoint, it is preferable to be 2 × 10 ^-4 or more. From the above viewpoints, the value of the in-plane birefringence (Δn) of the insulating resin layer is preferably in a range of 2 × 10 ^-4 or more and 8 × 10 ^-4 or less, and more preferably 2 × 10 ^-4 or more and 6 × 10 ^-4 or less.

Regarding the condition (ii), if the deviation [Δ (Δn)] of Δn in the TD direction exceeds 4 × 10 ^-4 , the deviation of the in-plane orientation becomes large, and this causes the in-plane deviation of the dimensional change rate. The deviation [Δ (Δn)] of Δn in the TD direction is preferably 2 × 10 ^-4 or less, and more preferably 1.2 × 10 ^-4 or less. Within such a range, high dimensional accuracy can be maintained, for example, even when scaled up.

In addition, regarding condition (iii), the difference (Δnh-Δn) in the value of the in-plane birefringence (Δn) before and after heating is ± 2 × 10 ^-4 or less, so that the directions of the in-plane orientation are maintained before and after heating. Isotropic, so that dimensional changes caused by heating can be suppressed. The difference (Δnh-Δn) in the value of the in-plane birefringence (Δn) before and after heating is preferably ± 1.2 × 10 ^-4 or less, and more preferably ± 0.8 × 10 ^-4 or less.

By satisfying the conditions (i) to (iii), the orientation of the polyimide constituting the insulating resin layer is improved, and a dimensional change due to heating can be suppressed, so that the dimensional stability is improved.

In addition, regarding the condition (iv) and the condition (v), the difference in birefringence (Δna-Δnb) in the thickness direction of the non-thermoplastic polyimide layer is ± 0.01 or less, and the Δna and Δnb and the average The difference (Δnv-Δna) and the difference (Δnv-Δnb) of the value (Δnv) are both ± 0.01 or less, whereby the homogeneity of the polyimide orientation in the thickness direction is improved, and the occurrence of warpage can be suppressed. Both the difference (Δnv-Δna) and the difference (Δnv-Δnb) are preferably ± 0.008 or less, and more preferably ± 0.006 or less.

In addition, by satisfying the conditions (i) and (ii) and (iv) and (v), the orientation of the polyimide constituting the insulating resin layer is improved, the dimensional stability is improved, and the warpage is improved. Occurrence is suppressed.

In addition, regarding the conditions (vi) and (vii), if the moisture absorption rate of the insulating resin layer becomes high, there is a problem that dimensional changes or warpage are liable to occur due to environmental changes such as temperature and pressure. Figure 1 shows two types of resins with different changes in moisture absorption rate and moisture absorption rate per unit time. After drying at 80 ° C for 1 hour, the changes in moisture absorption rate are shown at 23 ° C and 50% RH. chart. In the comparison of the two resins showing the hygroscopic characteristics as shown in FIG. 1, the following insights were obtained: a resin having not only a small hygroscopic rate but also a small hygroscopic rate change per unit time (A _m2- A _m1 ) with respect to size It is more effective to reduce variation or warpage. Therefore, by satisfying the conditions (vi) and (vii), it is possible to suppress dimensional changes caused by environmental changes (for example, high-temperature, high-pressure environments, humidity changes, etc.) during the circuit processing step, the substrate stacking step, and the component mounting step. Or warping. When the A _m exceeds 1.0% by weight or (A _m2- A _m1 ) exceeds 0.2% by weight, due to high temperature, high pressure, and humidity changes during the circuit processing step, the substrate lamination step, and the component mounting step, etc. The amount of dimensional change becomes large, the dimensional accuracy decreases, or warpage occurs.

It is effective by satisfying the condition (i) and the condition (ii), and satisfying the condition (iii), or both the condition (iv) and the condition (v), or both the condition (vi) and the condition (vii). It is possible to suppress dimensional changes or warpage caused by environmental changes (for example, high-temperature, high-pressure environments, humidity changes, etc.) during the circuit processing step, the substrate stacking step, and the component mounting step. On the other hand, if the combination of condition (i) and condition (ii) and condition (iii) is not available, or the combination of condition (i) and condition (ii) and condition (iv) and condition (v), or condition ( In the case of any combination of i) and condition (ii) and condition (vi) and condition (vii), due to high temperature, high pressure, humidity change, etc. during the circuit processing step, the substrate lamination step, and the component mounting step, The amount of dimensional change becomes large, the dimensional accuracy decreases, or warpage occurs.

In the case where the metal-clad laminate according to this embodiment is applied as a circuit board material, for example, in order to prevent occurrence of warpage or reduction in dimensional stability, it is important that the coefficient of thermal expansion (CTE) of the insulating resin layer is The range of 10 ppm / K or more and 30 ppm / K or less is preferable, and the range of 10 ppm / K or more and 25 ppm / K or less is preferable. When the CTE is less than 10 ppm / K or exceeds 30 ppm / K, warpage occurs or the dimensional stability decreases. In addition, in the metal-clad laminate of the present embodiment, the CTE of the insulating resin layer is more preferably within a range of ± 5 ppm / K, and most preferably within a range of ± 2 ppm / K, relative to the CTE of a metal layer including a copper foil. Within range.

In the insulating resin layer, the non-thermoplastic polyimide layer constitutes a low-thermal-expansion polyimide layer, and the thermoplastic polyimide layer constitutes a high-thermal-expansion polyimide layer. Here, the low-thermal-expansion polyimide layer means that the thermal expansion coefficient (CTE) is preferably within a range of 1 ppm / K or more and 25 ppm / K or less, and more preferably within a range of 3 ppm / K or more and 25 ppm / K or less. Polyimide layer. The high thermal expansion polyimide layer means that the CTE is preferably 35 ppm / K or more, more preferably 35 ppm / K or more and 80 ppm / K or less, and further preferably 35 ppm / K or more and 70 ppm / K. A polyimide layer within the following range. The polyimide layer can be made into a polyimide layer having a desired CTE by appropriately changing the combination of raw materials used, thickness, and drying and curing conditions.

The thickness of the insulating resin layer can be set to a thickness within a predetermined range according to the purpose of use. For example, the thickness is preferably in a range of 4 μm to 50 μm, and more preferably in a range of 11 μm to 26 μm. If the thickness of the insulating resin layer is less than the lower limit, electrical insulation properties may not be ensured, or problems such as difficulty in handling in manufacturing steps due to reduced workability may occur. On the other hand, if the thickness of the insulating resin layer exceeds the upper limit value, in order to control the in-plane birefringence (Δn) or the birefringence in the thickness direction, it is necessary to control the manufacturing conditions with high accuracy, resulting in a decrease in productivity, etc. Bad condition.

In addition, in the insulating resin layer, the thickness ratio ((A) / (B)) of the thickness (A) of the non-thermoplastic polyimide layer to the thickness (B) of the thermoplastic polyimide layer is preferably in the range of 1 to 20. It is more preferably within a range of 2 to 12. When the number of layers of the non-thermoplastic polyimide layer and / or the thermoplastic polyimide layer is plural, the thickness (A) or the thickness (B) refers to the total thickness. If the value of the ratio is less than 1, the non-thermoplastic polyimide layer becomes thinner than the entire insulating resin layer, so the deviation of the in-plane birefringence (Δn) tends to be large. If the value of the ratio exceeds 20 , The thermoplastic polyimide layer becomes thin, so the reliability of adhesion between the insulating resin layer and the metal layer is easily reduced. Here, the control of the in-plane birefringence (Δn) is related to the resin composition and thickness of each polyimide layer constituting the insulating resin layer. Regarding a thermoplastic polyimide layer composed of a resin that imparts adhesion, that is, high thermal expansion or softening, the larger the thickness, the greater the influence on the value of Δn of the insulating resin layer. Therefore, it is preferable to increase the ratio of the thickness of the non-thermoplastic polyimide layer, reduce the ratio of the thickness of the thermoplastic polyimide layer, and reduce the value of Δn of the insulating resin layer and its deviation. As described later, in this embodiment, the thermoplastic polyimide layer is designed to contain a predetermined amount selected from the general formula (2) and the thermoplastic polyimide layer even when the ratio of the thickness of the thermoplastic polyimide layer is reduced. The diamine residue in the general formula (3) can ensure the adhesion between the metal layer and the insulating resin layer.

From the viewpoint that the improvement effect of the dimensional accuracy of the insulating resin layer is more exhibited, the metal-clad laminate of the present embodiment preferably has a length (film width) in the width direction (TD direction) of 490 mm or more and 1200 or more. A range of not more than mm, more preferably a range of not less than 520 mm and not more than 1100 mm, and the length of the strip is 20 m or more. When the metal-clad laminate according to this embodiment is continuously manufactured, the wider the width direction (TD direction), the more significant the effect of the invention becomes. In addition, after continuously manufacturing the metal-clad laminate according to the present embodiment, slitting is performed at a certain value in the longitudinal direction (machine direction (MD) direction) and the TD direction of the long metal-clad laminate (slit). ) The resulting metal-clad laminate.

In addition, when the insulating resin layer is made of a polyfluorene imide film, the tensile elastic coefficient is preferably in a range of 3.0 GPa to 10.0 GPa, and more preferably in a range of 4.5 GPa to 8.0 GPa. If the polyimide film has a tensile elasticity of less than 3.0 GPa, the strength of the polyimide itself will be reduced. Therefore, when a metal-clad laminate is processed into a circuit board, an insulating resin layer may be produced. Operation problems such as cracking. Conversely, if the tensile modulus of elasticity when the polyimide film is made exceeds 10.0 GPa, the rigidity of the metal-clad laminate against bending is increased. As a result, when the metal-clad laminate is bent, the metal wiring is applied. The bending stress increases and the bending resistance decreases. By setting the coefficient of tensile elasticity when the polyfluorene film is made to be within the above range, the strength and flexibility of the insulating resin layer can be ensured.

(Non-thermoplastic polyimide) In this embodiment, it is preferable that the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, and these residues each include an aromatic substance. Family base. Since the tetracarboxylic acid residues and diamine residues contained in the non-thermoplastic polyfluorene imide contain aromatic groups, the order structure of the non-thermoplastic polyfluorene imine is easily formed, and the resistance of the insulating resin layer to high temperature environments is suppressed. The amount of change in the in-plane birefringence (Δn) reduces the difference (Δnh-Δn) between the values of the in-plane birefringence (Δn) before and after heating, and suppresses the deviation of the in-plane birefringence (Δn). Furthermore, changes in the birefringence in the thickness direction can be suppressed.

In the present invention, the term "tetracarboxylic acid residue" means a tetravalent group derived from a tetracarboxylic dianhydride, and the term "diamine residue" means a divalent group derived from a diamine compound. In the “diamine compound”, a hydrogen atom in two terminal amino groups may be substituted, and may be, for example, -NR ₃ R ₄ (here, R ₃ and R ₄ independently represent an arbitrary substituent such as an alkyl group).

The tetracarboxylic acid residue contained in the non-thermoplastic polyimide is not particularly limited, and for example, preferably, a tetracarboxylic acid residue derived from pyromellitic dianhydride (PMDA) (hereinafter also referred to as As PMDA residues), tetracarboxylic acid residues derived from 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (3,3', 4,4'-biphenyl tetracarboxylic dianhydride, BPDA) (Hereinafter also referred to as BPDA residues). These tetracarboxylic acid residues easily form an ordered structure, can suppress the amount of change in in-plane birefringence (Δn) under high temperature environment, and reduce the difference (Δnh-Δn) of the value of in-plane birefringence (Δn) before and after heating. ). Furthermore, changes in the birefringence in the thickness direction can be suppressed. The PMDA residue is a residue that functions to control the coefficient of thermal expansion and the glass transition temperature. Furthermore, as for the BPDA residue, since no polar group exists in the tetracarboxylic acid residue and the molecular weight is relatively large, the effect of reducing the concentration of the fluorene imine group of the non-thermoplastic polyfluorene imine and suppressing the moisture absorption of the insulating resin layer can also be expected. . From this point of view, the total amount of PMDA residues and / or BPDA residues is preferably 50 mol parts or more relative to 100 mol parts of all tetracarboxylic acid residues contained in the non-thermoplastic polyimide. It is preferably in the range of 50 to 100 mol parts, and most preferably in the range of 70 to 100 mol parts.

Examples of other tetracarboxylic acid residues contained in non-thermoplastic polyimide include tetracarboxylic acid residues derived from the following aromatic tetracarboxylic dianhydrides: 2,3 ', 3,4'-biphenyltetra Carboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 4,4'-oxybis Phthalic anhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, or 3,3 ' , 4,4'-benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4'-diphenyl ether tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride , 3,3 '', 4,4 ''-p-terephthalate dianhydride, 2,3,3 '', 4 ''-p-terephthalate dianhydride or 2,2 '', 3 , 3 ''-p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride or 2,2-bis (3,4-dicarboxyphenyl)- Propane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride or bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) fluorene dianhydride or bis (3,4-dicarboxyphenyl) pyrene dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, or 1,1-bis (3,4-dicarboxyphenyl) ethyl Alkane dianhydride, 1,2,7,8-phenanthrene-tetracarboxylic dianhydride, 1,2,6,7-phenanthrene-tetracarboxylic dianhydride or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride Acid dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane Alkane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4 , 8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5 , 8-tetracarboxylic dianhydride or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8 -Tetracarboxylic dianhydride or 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,3,8,9-fluorene-tetracarboxylic dianhydride, 3 , 4,9,10-fluorene-tetracarboxylic dianhydride, 4,5,10,11-fluorene-tetracarboxylic dianhydride or 5,6,11,12-fluorene-tetracarboxylic dianhydride, cyclopentane -1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene -2,3,4,5-tetracarboxylic dianhydride, 4,4'-bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride, and the like.

As a diamine residue contained in a non-thermoplastic polyfluorene imide, the diamine residue derived from the diamine compound represented by General formula (1) is mentioned preferably.

[Chemical 3]

In the general formula (1), the linking group Z represents a single bond or -COO-, and Y independently represents a monovalent hydrocarbon having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom or a phenyl group. Or a perfluoroalkyl group or an alkenyl group having 1 to 3 carbon atoms, n represents an integer of 0 to 2, and p and q independently represent an integer of 0 to 4. Here, "independently" means that in the formula (1), a plurality of substituents Y, integer p, and integer q may be the same or different.

The diamine residue (hereinafter, sometimes referred to as "diamine residue (1)") derived from the diamine compound represented by the general formula (1) easily forms an ordered structure, improves dimensional stability, and is effective It is possible to suppress the amount of change in the in-plane birefringence (Δn), especially in a high-temperature environment, and to reduce the difference (Δnh-Δn) in the value of the in-plane birefringence (Δn) before and after heating. Furthermore, it is possible to effectively suppress a change in birefringence in the thickness direction. From this point of view, the diamine residue (1) is 100 mol parts or more, preferably 70 mol parts to 95 mol parts relative to all the diamine residues contained in the non-thermoplastic polyimide. The content is preferably in the range of moles, more preferably in the range of 80 to 90 moles.

Preferred specific examples of the diamine residue (1) include diamine residues derived from the following diamine compounds: p-phenylenediamine (p-PDA), 2,2'-dimethyl-4,4 ' -Diaminobiphenyl (m-TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB), 2 , 2'-diethoxy-4,4'-diaminobiphenyl (2,2'-diethoxy-4,4'-diaminobiphenyl, m-EOB), 2,2'-dipropoxy-4, 4'-diaminobiphenyl (2,2'-dipropoxy-4,4'-diaminobiphenyl, m-POB), 2,2'-n-propyl-4,4'-diaminobiphenyl (2,2 ' -n-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2'-divinyl-4,4'-diaminobiphenyl (2,2'-divinyl-4,4'-diaminobiphenyl, VAB), 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (4,4'-diamino-2,2'-bis ( trifluoromethyl) biphenyl, TFMB), etc. Among these diamine compounds, in particular, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) easily forms an order structure, and can suppress in-plane birefringence (Δn) in a high-temperature environment. It is particularly preferable to reduce the amount of change in in-plane birefringence (Δn) before and after heating by reducing the difference (Δnh-Δn) in the value of the birefringence, and to suppress the change in birefringence in the thickness direction.

In addition, in order to reduce the coefficient of elasticity of the insulating resin layer and improve elongation and bending resistance, it is preferable that the non-thermoplastic polyimide contains two selected from the group consisting of two represented by the following general formula (2) and general formula (3) At least one diamine residue in the group of amine residues.

[Chemical 4]

In the formulas (2) and (3), R ₅ , R ₆ , R ₇ and R ₈ each independently represent a halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms which may be substituted with a halogen atom. , Or alkenyl, X independently represents selected from -O-, -S-, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CO-, -COO-,- Divalent group in SO _2- , -NH- or -NHCO-, X ₁ and X ₂ each independently represent a single bond and are selected from -O-, -S-, -CH _2- , -CH (CH ₃ ) -, -C (CH ₃ ) _2- , -CO-, -COO-, -SO _2- , -NH- or -NHCO-, but both X ₁ and X ₂ are single bond Except in this case, m, n, o, and p independently represent integers of 0 to 4. In addition, "independently" means that in one or both of the formulae (2) and (3), a plurality of linking groups X, a linking group X ₁ and a linking group X ₂ , and a plurality of substituents R ₅ , substituent R ₆ , substituent R ₇ , substituent R ₈ , and further integer m, integer n, integer o, and integer p may be the same or different.

Since the diamine residues represented by the general formula (2) and the general formula (3) have a flexible portion, flexibility can be imparted to the insulating resin layer. Here, since the diamine residue represented by the general formula (3) has four benzene rings, in order to suppress an increase in the coefficient of thermal expansion (CTE), it is preferable to set the terminal group bonded to the benzene ring to the para position. In addition, from the viewpoint of imparting flexibility to the insulating resin layer and suppressing an increase in the coefficient of thermal expansion (CTE), the diamine residues represented by the general formula (2) and the general formula (3) are relatively larger than those of the non-thermoplastic polyamide. It is preferable that all the diamine residues contained in the amine are contained in a range of 100 mol parts, preferably 5 mol parts to 30 mol parts, and more preferably 10 mol parts to 20 mol parts. If the diamine residues represented by the general formula (2) and the general formula (3) are less than 5 mol parts, the elastic modulus of the insulating resin layer may increase, the elongation may decrease, and a reduction in bending resistance and the like may occur. When the diamine residue represented by the general formula (2) and the general formula (3) exceeds 30 mol parts, the molecular orientation may decrease, and it may become difficult to reduce CTE.

The diamine residue represented by the general formula (2) is preferably one in which one or more of m, n, and o are 0, and preferable examples of the group R ₅ , the group R _6, and the group R ₇ include: carbon number 1 to An alkyl group which may be substituted by a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. Examples of preferred examples of the linking group X in the general formula (2) include -O-, -S-, -CH _2- , -CH (CH ₃ )-, -SO _2- , or -CO-. Preferred specific examples of the diamine residue represented by the general formula (2) include diamine residues derived from the following diamine compounds: 1,3-bis (4-aminophenoxy) benzene (TPE-R ), 1,4-bis (4-aminophenoxy) benzene (1,4-bis (4-aminophenoxy) benzene, TPE-Q), bis (4-aminophenoxy) -2,5-di- Tert-butylbenzene (bis (4-aminophenoxy) -2,5-di-tert-butyl benzene (DTBAB), 4,4-bis (4-aminophenoxy) benzophenone (4,4-bis ( 4-aminophenoxy) benzophenone (BAPK), 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4-aminophenyl) -2- Propyl] benzene and the like.

The diamine residue represented by the general formula (3) is preferably one in which one or more of m, n, o, and p are 0, and preferable examples of the group R ₅ , the group R ₆ , the group R _7, and the group R ₈ may be Examples include an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. In the general formula (3), preferred examples of the linking group X ₁ and the linking group X ₂ include a single bond, -O-, -S-, -CH _2- , -CH (CH ₃ )-, -SO. ₂ -or-CO-. However, from the viewpoint of providing a bent portion, the case where both the linking group X ₁ and the linking group X ₂ are single bonds is excluded. Preferred specific examples of the diamine residue represented by the general formula (3) include diamine residues derived from the following diamine compounds: 4,4'-bis (4-aminophenoxy) biphenyl (4 , 4'-bis (4-aminophenoxy) biphenyl (BAPB), 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), 2,2'-bis [4- ( 4-aminophenoxy) phenyl] ether (2,2'-bis [4- (4-aminophenoxy) phenyl] ether, BAPE), bis [4- (4-aminophenoxy) phenyl] fluorene, etc. .

Among the diamine residues represented by the general formula (2), particularly preferred are diamine residues derived from 1,3-bis (4-aminophenoxy) benzene (TPE-R) (sometimes referred to as "TPE -R residue "), among the diamine residues represented by the general formula (3), particularly preferably derived from 2,2'-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) Diamine residues (sometimes referred to as "BAPP residues"). Since the TPE-R residue and the BAPP residue have a flexible portion, the elastic modulus of the insulating resin layer can be reduced, and flexibility can be imparted. In addition, since the molecular weight of the BAPP residue is large, the effect of reducing the fluorene imine group concentration of the non-thermoplastic polyfluorene imine and suppressing the moisture absorption of the insulating resin layer can also be expected.

Examples of other diamine residues contained in the non-thermoplastic polyimide include diamine residues derived from the following aromatic diamine compounds: m-phenylenediamine (m-PDA), 4, 4 '-Diaminodiphenyl ether (4,4'-diamino diphenyl ether, DAPE), 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 3,3'-diamino Diphenylpropane, 3,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 3,4'-diamino Diphenyl sulfide, 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminobenzophenone, 3,4'-diaminodiamine Benzophenone, 3,3'-diaminobenzophenone, 2,2-bis- [4- (3-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) Phenyl] fluorene, bis [4- (3-aminophenoxy) biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (3-aminophenoxy) phenyl ] Methane, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy)] diphenyl Methyl ketone, 9,9-bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2-bis- [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2, 2-bis- [4- (3-aminophenoxy) phenyl] hexafluoropropane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebis -O-Toluidine, 4,4'-methylenebis-2,6-dimethyltoluidine, 4,4'-methylene-2,6-diethylaniline, 3,3'-diaminodiphenyl Ethane, 3,3'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 3,3 ''-diamino-p-terphenyl, 4,4 '-[1,4- Phenylbis (1-methylethylene)] bisaniline, 4,4 '-[1,3-phenylenebis (1-methylethylene)] bisaniline, bis (p-aminocyclohexyl) Methane, bis (p-β-amino-tert-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) benzene, p- Bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis (β-amino-tert-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, verazine and the like.

In the non-thermoplastic polyimide, each mole is selected by selecting the type of the tetracarboxylic acid residue and the diamine residue, or when two or more kinds of the tetracarboxylic acid residue or the diamine residue are used. Ratio, can control thermal expansion coefficient, storage elastic coefficient, tensile elastic coefficient and so on. In addition, in the case where the non-thermoplastic polyfluorene imine has a plurality of structural units of polyfluorene, it can exist in the form of a block, or it can also exist randomly, from the suppression of the in-plane birefringence (Δn). From the viewpoint of deviation, it is preferable to exist randomly.

The concentration of the fluorene imine group of the non-thermoplastic polyfluorene imine is preferably 35% by weight or less. Here, the "fluorene imino group concentration" refers to a value obtained by dividing the molecular weight of the fluorene imino moiety (-(CO) ₂ -N-) in the polyfluorene imide by the molecular weight of the entire structure of the polyfluorene imine. When the fluorene imine group concentration exceeds 35% by weight, the molecular weight of the resin itself becomes small, and low hygroscopicity is also deteriorated due to an increase in the polar group. By selecting the combination of the acid anhydride and the diamine compound to control the orientation of the molecules in the non-thermoplastic polyimide, thereby suppressing the increase in the CTE accompanied by the decrease in the concentration of the imino group, thereby ensuring low hygroscopicity.

The weight average molecular weight of the non-thermoplastic polyimide is preferably in the range of 10,000 to 400,000, and more preferably in the range of 50,000 to 350,000. When the weight-average molecular weight is less than 10,000, the strength of the insulating resin layer tends to decrease and tends to become brittle. On the other hand, when the weight average molecular weight exceeds 400,000, viscosity tends to increase excessively, and defects such as uneven thickness and streaks tend to occur during the coating operation.

(Thermoplastic polyimide) In this embodiment, it is preferable that the thermoplastic polyimide constituting the thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, and these residues each include an aromatic group. Since both the tetracarboxylic acid residue and the diamine residue contained in the thermoplastic polyimide contain aromatic groups, the amount of change in the in-plane birefringence (Δn) of the insulating resin layer under a high-temperature environment can be suppressed and reduced. The difference (Δnh-Δn) between the values of the in-plane birefringence (Δn) before and after the heating is small. Furthermore, changes in the birefringence in the thickness direction can be suppressed.

The tetracarboxylic acid residue contained in the thermoplastic polyimide is not particularly limited. For example, a tetracarboxylic acid residue derived from pyromellitic dianhydride (PMDA) (hereinafter also referred to as a PMDA residue) may be preferably cited. ), A tetracarboxylic acid residue derived from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) (hereinafter also referred to as a BPDA residue). These tetracarboxylic acid residues easily form an ordered structure, can suppress the amount of change in in-plane birefringence (Δn) in a high-temperature environment, and reduce the difference in in-plane birefringence (Δn) values before and after heating (Δnh-Δn ). Furthermore, changes in the birefringence in the thickness direction can be suppressed. The PMDA residue is a residue that functions to control the coefficient of thermal expansion and the glass transition temperature. Furthermore, as for the BPDA residue, since a polar group does not exist in the tetracarboxylic acid residue and the molecular weight is relatively large, the effect of reducing the fluorene imine group concentration of the thermoplastic polyfluorene imine and suppressing the moisture absorption of the insulating resin layer can also be expected. From this viewpoint, the total amount of PMDA residues and / or BPDA residues is preferably 50 mol parts or more, more preferably 100 mol parts or more, relative to 100 mol parts of all tetracarboxylic acid residues contained in the thermoplastic polyimide. It is preferably in the range of 50 to 100 mol parts, and most preferably in the range of 70 to 100 mol parts.

Examples of other tetracarboxylic acid residues contained in the thermoplastic polyfluorene imide include tetracarboxylic acid residues derived from the same aromatic tetracarboxylic dianhydride as exemplified in the non-thermoplastic polyfluorene imine.

In the present embodiment, the diamine residue contained in the thermoplastic polyfluorene imine is preferably at least one diamine residue selected from the general formula (2) and the general formula (3). The diamine residues selected from the general formulae (2) and (3) are preferably 50 mol parts or more in total, and more preferably 50 mol parts to 100 mol parts with respect to 100 mol parts of all diamine residues. The amount of ears is most preferably in the range of 70 to 100 moles. The thermoplastic polyfluorene imide layer can be formed by including a total of 50 mol parts or more of diamine residues selected from the general formula (2) and the general formula (3) with respect to 100 mol parts of all diamine residues. Provides flexibility and adhesion, and makes it function as an adhesion layer to a metal layer. Among the diamine residues represented by the general formula (2), TPE-R residues are particularly preferred, and among the diamine residues represented by the general formula (3), BAPP residues are particularly preferred. Since the TPE-R residue and the BAPP residue have a flexible portion, the elastic modulus of the insulating resin layer can be reduced and flexibility can be imparted. In addition, since the molecular weight of the BAPP residue is large, the effect of reducing the fluorene imine group concentration of the thermoplastic polyfluorene imine and suppressing the moisture absorption of the insulating resin layer can also be expected.

In addition, as described above, when the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains a diamine residue selected from the general formula (2) and the general formula (3), the thermoplastic polyfluorene is constituted. As the diamine residue, the thermoplastic polyfluorene imine of the imine layer is preferably a diamine residue having a similar structure, and preferably the same type of diamine residue selected from the general formula (2) and the general formula (3). In this case, the content ratios of the diamine residues in the thermoplastic polyimide and the non-thermoplastic polyimide are different, but are formed by containing similar or the same diamine residues, especially by the cast method. In the case of a polyimide film, it is easy to control the orientation of the thermoplastic polyimide layer and the non-thermoplastic polyimide layer, and it is easy to manage the dimensional accuracy. From such a viewpoint, it is preferable in this embodiment that both the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer and the thermoplastic polyimide constituting the thermoplastic polyimide layer contain Said at least one diamine residue in the general formula (2) and the general formula (3), the diamine residue most preferably contains a TPE-R residue and / or a BAPP residue.

In the present embodiment, examples of the diamine residues other than the general formula (2) and the general formula (3) contained in the thermoplastic polyfluorene imine include diamine residues derived from the following diamine compounds: 2 , 2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB), 2,2 '-Diethoxy-4,4'-diaminobiphenyl (m-EOB), 2,2'-dipropoxy-4,4'-diaminobiphenyl (m-POB), 2,2 '-N-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2'-divinyl-4,4'-diaminobiphenyl (VAB), 4,4'-diamino Biphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (TFMB), p-phenylenediamine (p-PDA), m-phenylenediamine (m- PDA), 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl Hydrazone, 3,3-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylpropane, 3 , 4'-diaminodiphenylsulfide, 3,3'-diaminobenzophenone, (3,3'-bisamino) diphenylamine, 1,4-bis (3-aminophenoxy ) Benzene, 3- [ 4- (4-aminophenoxy) phenoxy] aniline, 3- [3- (4-aminophenoxy) phenoxy] aniline, 1,3-bis (3-aminophenoxy) benzene ( 1,3-bis (3-aminophenoxy) benzene (APB), 4,4 '-[2-methyl- (1,3-phenylene) dioxy] bisaniline, 4,4'-[4- Methyl- (1,3-phenylene) dioxy] bisaniline, 4,4 '-[5-methyl- (1,3-phenylene) dioxy] bisaniline, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] ether, bis [4 -(3-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy)] benzophenone, bis [4,4 '-(3-aminophenoxy)] benzoyl Aniline, 4- [3- [4- (4-aminophenoxy) phenoxy] phenoxy] aniline, 4,4 '-[oxybis (3,1-phenyleneoxy)] Bisaniline, bis [4- (4-aminophenoxy) phenyl] ether (BAPE), bis [4- (4-aminophenoxy) phenyl] ketone (BAPK), bis [4- (3- Aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy)] biphenyl and the like.

In the thermoplastic polyfluorene imine, the respective mole ratios in the case where two or more kinds of tetracarboxylic acid residues or diamine residues are used are selected by the types of the tetracarboxylic acid residues and diamine residues. , Can control the coefficient of thermal expansion, tensile modulus of elasticity, glass transition temperature and so on. In addition, in the case where the thermoplastic polyfluorene imide has a plurality of structural units of the polyfluorene imine, it may exist in the form of a block or may exist randomly, and preferably it exists randomly.

The thermoplastic polyimide constituting the thermoplastic polyimide layer can improve the adhesion to the metal layer. The glass transition temperature of such a thermoplastic polyimide is in a range of 200 ° C to 350 ° C, and preferably in a range of 200 ° C to 320 ° C.

The fluorene imine group concentration of the thermoplastic polyfluorene imide is preferably 35% by weight or less. Here, the "fluorene imino group concentration" refers to a value obtained by dividing the molecular weight of the fluorene imino moiety (-(CO) ₂ -N-) in the polyfluorene imide by the molecular weight of the entire structure of the polyfluorene imine. When the fluorene imine group concentration exceeds 35% by weight, the molecular weight of the resin itself becomes small, and low hygroscopicity is also deteriorated due to an increase in the polar group. By selecting the combination of the acid anhydride and the diamine compound to control the orientation of the molecules in the thermoplastic polyfluorene imine, thereby suppressing the increase in CTE accompanied by a decrease in the concentration of the fluorene imino group, thereby ensuring low hygroscopicity.

The weight average molecular weight of the thermoplastic polyimide is, for example, preferably in the range of 10,000 to 400,000, and more preferably in the range of 50,000 to 350,000. When the weight average molecular weight is less than 10,000, the strength of the insulating resin layer tends to decrease, and tends to become brittle. On the other hand, when the weight average molecular weight exceeds 400,000, viscosity tends to increase excessively, and defects such as uneven thickness and streaks tend to occur during the coating operation.

(Synthesis of Non-Thermoplastic Polyimide and Thermoplastic Polyimide) Generally, polyimide can be produced by reacting a tetracarboxylic dianhydride with a diamine compound in a solvent to generate polyimide Closed loop heating. For example, a tetracarboxylic dianhydride and a diamine compound are dissolved in an organic solvent at approximately equal moles, and the polymerization reaction is performed by stirring at a temperature in a range of 0 ° C to 100 ° C for 30 minutes to 24 hours, thereby obtaining Polyamidic acid, a precursor of polyimide. At the time of the reaction, the generated precursor is dissolved in an organic solvent in a range of 5% to 30% by weight, preferably in a range of 10% to 20% by weight. Examples of the organic solvent used in the polymerization reaction include: N, N-dimethyl formamide (DMF), N, N-dimethyl acetamide (N, N-dimethyl acetamide) DMAc), N, N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2-butanone, dimethyl sulfoxide (DMSO ), Hexamethylphosphoramidine, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, diglyme Ether (triglyme), cresol, etc. These solvents may be used in combination of two or more kinds, and an aromatic hydrocarbon such as xylene and toluene may also be used in combination. In addition, the amount of such organic solvents used is not particularly limited, and it is preferred to adjust the use amount such that the concentration of the polyamic acid solution obtained by the polymerization reaction becomes about 5% to 30% by weight.

The synthesized polyamidic acid is usually advantageously used in the form of a reaction solvent solution, which can be concentrated, diluted or replaced with other organic solvents as needed. In addition, polyamic acid is generally excellent in solvent solubility, and thus can be favorably used. The viscosity of the polyamic acid solution is preferably in the range of 500 cps to 100,000 cps. If it deviates from the said range, when a coating operation is performed with a coater or the like, defects such as uneven thickness and streaks are likely to occur in the film. The method of polyimidizing polyamic acid is not particularly limited. For example, heat treatment such as heating in the solvent at a temperature in a range of 80 ° C. to 400 ° C. for 1 hour to 24 hours is suitably used.

<Metal layer> Examples of the metal constituting the metal layer include copper, aluminum, stainless steel, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zirconium, gold, cobalt, titanium, tantalum, zinc, lead, tin, Metals in silicon, bismuth, indium, or alloys thereof. The metal layer can also be formed by methods such as sputtering, vapor deposition, and plating, but from the viewpoint of adhesion, it is preferable to use a metal foil. Particularly preferred is copper foil in terms of conductivity. The copper foil may be any one of an electrolytic copper foil and a rolled copper foil. In the case where the metal-clad laminate according to the present embodiment is continuously produced, a long-shaped metal foil obtained by winding a person having a predetermined thickness into a roll shape is used as the metal foil.

Hereinafter, as a preferred embodiment of the metal-clad laminate, a copper-clad laminate having a copper layer will be described.

<Copper-clad laminate> The copper-clad laminate according to the present embodiment may include an insulating layer and a copper layer such as a copper foil on at least one surface of the insulating layer. In addition, in order to improve the adhesion between the insulating layer and the copper layer, the layer in contact with the copper layer in the insulating layer is a thermoplastic polyimide layer. The copper layer is disposed on one or both sides of the insulating layer. That is, the copper-clad laminate according to this embodiment may be a single-sided copper-clad laminate (single-sided CCL) or a double-sided copper-clad laminate (double-sided CCL). In the case of a single-sided CCL, a copper layer laminated on one surface of an insulating layer is referred to as a "first copper layer" in the present invention. In the case of a double-sided CCL, the copper layer laminated on one side of the insulating layer is referred to as the “first copper layer” in the present invention, and the layer laminated on the insulating layer is opposite to the surface on which the first copper layer is laminated. The copper layer on the surface is the "second copper layer" in the present invention. The copper-clad laminate according to the present embodiment is formed by etching a copper layer and performing wiring circuit processing to form a copper wiring, and is used as an FPC.

For example, a copper-clad laminate can be prepared by preparing a resin film and sputtering a metal to form a seed layer, and then, for example, forming a copper layer by copper plating.

In addition, a copper-clad laminate can also be prepared by preparing a resin film and laminating a copper foil thereto by a method such as thermocompression bonding.

Furthermore, a copper-clad laminate can also be prepared by casting a coating solution containing polyamic acid as a precursor of polyimide on a copper foil, drying the coating solution, forming a coating film, and then performing a heat treatment to obtain a coating film. Imidization, thereby forming a polyfluorene imine layer.

(First Copper Layer) In the copper-clad laminate according to the present embodiment, the copper foil (hereinafter, sometimes referred to as “first copper foil”) used in the first copper layer is not particularly limited, and may be, for example, rolled copper. The foil may be electrolytic copper foil.

The thickness of the first copper foil is preferably within a range of 13 μm or less, and more preferably 6 μm to 12 μm. When the thickness of the first copper foil exceeds 13 μm, the bending stress applied to the copper layer (or copper wiring) when the copper-clad laminate (or FPC) is bent is increased, and thus the bending resistance is reduced. In addition, from the viewpoint of production stability and operability, the lower limit value of the thickness of the first copper foil is preferably set to 6 μm.

The tensile elastic modulus of the first copper foil is preferably in a range of, for example, 10 GPa to 35 GPa, and more preferably in a range of 15 GPa to 25 GPa. In the case where a rolled copper foil is used as the first copper foil in the present embodiment, if annealing is performed by heat treatment, flexibility is easily increased. Therefore, if the tensile elastic coefficient of the copper foil is less than the lower limit value, in the step of forming an insulating layer on the long first copper foil, the rigidity of the first copper foil itself is reduced due to heating. On the other hand, if the tensile modulus of elasticity exceeds the upper limit value, a greater bending stress is applied to the copper wiring when the FPC is bent, and the bending resistance is reduced. In addition, the rolled copper foil tends to change its tensile elasticity coefficient according to heat treatment conditions when an insulating layer is formed on the copper foil, or annealing treatment of the copper foil after the insulating layer is formed. Therefore, in this embodiment, as long as the copper-clad laminated sheet finally obtained, the tensile elastic coefficient of the first copper foil is within the above range.

The first copper foil is not particularly limited, and a commercially available rolled copper foil can be used.

(Second Copper Layer) The second copper layer is laminated on the surface of the insulating layer on the side opposite to the first copper layer. The copper foil (second copper foil) used in the second copper layer is not particularly limited, and may be, for example, a rolled copper foil or an electrolytic copper foil. Alternatively, a commercially available copper foil may be used as the second copper foil. In addition, the same copper foil as the first copper foil may be used as the second copper foil.

<Circuit Board> The metal-clad laminate according to this embodiment is mainly useful as a material for a circuit board such as an FPC. For example, a circuit layer such as an FPC, which is an embodiment of the present invention, can be manufactured by processing a copper layer of the illustrated copper-clad laminate into a pattern by a common method to form a wiring layer.

[Examples] Examples will be described below to more specifically describe the features of the present invention. However, the scope of the present invention is not limited to the examples. In the following examples, unless otherwise specified, various measurements and evaluations are performed by the following methods.

[Measurement of Viscosity] For measurement of viscosity, the viscosity at 25 ° C. was measured using an E-type viscometer (trade name: DV-II + Pro manufactured by Brookfield). Set the rotation speed so that the torque becomes 10% to 90%. After 2 minutes from the start of the measurement, read the value when the viscosity is stable.

[Measurement of glass transition temperature (Tg)] As for the glass transition temperature, a dynamic viscoelasticity measuring device (DMA: trade name: E4000F manufactured by UBM Corporation) was used, and the temperature was raised from 30 ° C to 400 ° C at a temperature increase rate of 4 ° C / min, and the frequency was 11 A 5 mm × 20 mm size polyimide film was measured in Hz, and the temperature at which the change in elastic coefficient (tan δ) reached the maximum was taken as the glass transition temperature. In addition, those whose storage elastic modulus at 30 ° C measured by DMA is 1.0 × 10 ⁹ Pa or more and whose storage elastic modulus at 360 ° C shows less than 1.0 × 10 ⁸ Pa are regarded as “thermoplastic”, and those at 30 ° C are regarded as “thermoplastic”. A storage elasticity coefficient of 1.0 × 10 ⁹ Pa or more and a storage elasticity coefficient of 1.0 × 10 ⁸ Pa or more at 360 ° C. are regarded as “non-thermoplastic”.

[Measurement of Coefficient of Thermal Expansion (CTE)] Using a thermomechanical analyzer (trade name: 4000SA manufactured by Bruker), a polyimide film having a size of 3 mm × 20 mm was applied with a load of 5.0 g on one side The temperature was raised from 30 ° C to 265 ° C at a constant temperature increase rate, and the temperature was further maintained at the temperature for 10 minutes, and then cooled at a rate of 5 ° C / min to obtain an average thermal expansion coefficient (coefficient of thermal expansion) from 250 ° C to 100 ° C. .

[Measurement of in-plane retardation (RO)] A birefringence meter (Photonic-Lattice) was used: trade name: wide range birefringence evaluation system WPA-100, measurement area: MD: 140 mm × TD: 100 mm), and determine the retardation in the in-plane direction of a given sample. The incident angle was 0 °, and the measurement wavelength was 543 nm.

[Preparation of Evaluation Sample for In-Plane Delay (RO)] The left and right end portions in the TD direction (left (left (left)) of a polyimide film obtained by etching a metal layer of a long metal-clad laminate. Left) and Right) and the center (Center), respectively cut with A4 size (TD: 210 mm × MD: 297 mm) to prepare sample L (Left), sample R (Right) and sample C (Center ).

[Evaluation of in-plane birefringence (Δn)] In-plane retardation (RO) was measured for each of sample L, sample R, and sample C. The value obtained by dividing the maximum value of the measured value of each sample by the thickness of the evaluation sample is defined as "in-plane birefringence (Δn)", and the value of the maximum and minimum values among the measured values of the in-plane retardation (RO) is determined. The difference is "deviation (ΔRO) of in-plane retardation (RO) in the width direction (TD direction)", and the value obtained by dividing the ΔRO by the thickness of the evaluation sample is "in-plane in the width direction (TD direction)". Deviation of birefringence (Δn) [Δ (Δn)] ”.

[Evaluation of in-plane retardation (ROh) and in-plane birefringence (Δnh) after heating] A polyimide film obtained by etching a metal layer of a metal-clad laminate was prepared, and measured at 23 ° C and 50% RH The in-plane retardation (RO) of the sample after humidity for 24 hours in an environment. Then, this sample was heat-treated in a high-temperature environment at 250 ° C for 30 minutes, and the in-plane retardation (ROh) after heating was measured. The difference (| ROh-RO |) between the value of the in-plane retardation (ROh) after heating at 250 ° C for 30 minutes and the value of the in-plane retardation (RO) before heating was calculated. The value obtained by dividing the value of the in-plane retardation (RO) of the sample after humidity conditioning at 23 ° C and 50% RH for 24 hours divided by the thickness of the sample is set to "in-plane birefringence (Δn) before heating". , The value obtained by dividing the value of the in-plane retardation (ROh) after heating by the thickness of the sample is set to "in-plane birefringence (Δnh) after heating at 250 ° C for 30 minutes", and the in-plane retardation before and after heating The value of (RO) difference (| ROh-RO |) divided by the thickness of this sample is set to "the value of in-plane birefringence (Δnh) after heating at 250 ° C for 30 minutes and the in-plane birefringence before heating The difference in the value of the rate (Δn) (| Δnh-Δn |) ".

[Measurement of retardation in the thickness direction and birefringence] For a polyimide layer as an insulating resin layer, a thin slice with a thickness of 0.5 μm was produced by an ultra-thin sectioning method, and retardation measurement in the thickness direction was performed. At this time, a birefringence meter (trade name manufactured by Photonic-Lattice Co., Ltd .: birefringence profile observation camera for microscope mounting PI-micro) was used. The measurement wavelength was 520 nm, and the incident angle was 0 °. The ROa is a value of retardation at a point of 1.5 μm in the direction of the central portion of the non-thermoplastic polyimide layer in the polyimide layer (film) as a base point. The ROb is a value of retardation at a point of 1.5 μm in the direction of the central portion from the other surface of the non-thermoplastic polyimide layer in the polyimide layer (film) as a base point. The ROv is the total (ROa + ROb + ROc) of the retardation value (ROc) in the central portion in the thickness direction of the non-thermoplastic polyimide layer in the polyimide layer (film). average value. In addition, the value obtained by dividing the value of ROa by the thickness (0.5 μm) of the film slice was set to “a point 1.5 μm in the direction of the central portion of the non-thermoplastic polyimide layer in the direction of the thickness of one surface as a base point Birefringence (Δna) ", the value obtained by dividing the value of Rob by the thickness of the film slice (0.5 μm) is set to" the center of the non-thermoplastic polyimide layer in the thickness direction with the other surface as the base point " The birefringence (Δnb) at a point of 1.5 μm in the direction of the film ”, and the value obtained by dividing the value of Roc by the thickness (0.5 μm) of the film slice is defined as“ the central portion of the thickness direction of the non-thermoplastic polyimide layer ” Birefringence (Δnc) ". Δnv is an average value of the total (Δna + Δnb + Δnc) of Δna, Δnb, and Δnc.

[Measurement of moisture absorption (A _m1 , A _m2 , A _m )] A4 size (TD: 210 mm × MD: 297 mm) polyimide film was dried in a hot air oven at 80 ° C for 1 hour, and the drying was measured. This weight is taken as the dry weight (W1). After the polyimide film having measured the dry weight was allowed to absorb moisture for a predetermined time at a constant temperature and constant humidity of 23 ° C. and 50% RH, the weight was measured as the weight after moisture absorption (W2). Based on the measured weight, it was substituted into the following formula, and the moisture absorption rate was calculated. In addition, the moisture absorption rate (A _m ) is the moisture absorption rate after drying at 80 ° C. for 1 hour, and the humidity is adjusted at 23 ° C. and 50% RH for 4 hours, and the moisture absorption rate (A _m1 ) is at 80 ° C. After 1 hour of drying, the moisture absorption rate after humidity adjustment for 1 hour at 23 ° C and 50% RH constant temperature and humidity. The moisture absorption rate (A _m2 ) is after drying at 80 ° C for 1 hour, at 23 ° C and 50% RH. Moisture absorption rate after 2 hours of humidity control at constant temperature and humidity.

[Formula 1] Moisture absorption rate (% by weight) = (W2-W1) / W1

[Measurement of Warpage] After a polyimide film having a size of 50 mm × 50 mm was humidity-controlled at 23 ° C. and 50% RH for 24 hours, the direction of curl was set to the upper surface and set on a smooth table. The curl amount at this time was measured using a vernier caliper. At this time, a case where the film is curled toward the substrate etched surface side is described as plus, and a case where the film is curled toward the opposite surface is described as minus, and the average of the measured values of the four corners of the film is the curl amount.

[Measurement of Peel Strength] After a copper foil of a single-sided copper-clad laminate (copper foil / resin layer) was subjected to circuit processing with a width of 1.0 mm, it was cut with a width: 8 cm × length: 4 cm to prepare a measurement sample. Using a Tensilon tester (trade name: Strograph VE-1D manufactured by Toyo Seiki Seisakusho), the resin layer side of the measurement sample was fixed to an aluminum plate with a double-sided tape, and copper foil was used. Peeling was performed at a speed of 50 mm / min in the 90 ° direction, and the central strength when the copper foil was peeled from the resin layer by 10 mm was determined.

The abbreviations used in Examples and Comparative Examples indicate the following compounds. PMDA: pyromellitic dianhydride BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl TPE -R: 1,3-bis (4-aminophenoxy) benzene DAPE: 4,4'-diaminodiphenyl ether BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane p-PDA: p-phenylenediamine DMAc: N, N-dimethylacetamide

(Synthesis Example 1) Under a nitrogen flow, 23.0 parts by weight of m-TB (0.108 mol parts), 3.5 parts by weight of TPE-R (0.012 mol parts), and the solid content concentration after polymerization were 15 DMAc in an amount of% by weight was dissolved by stirring at room temperature. Next, after adding 26.0 parts by weight of PMDA (0.119 mol parts), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution a. The solution viscosity of the polyamic acid solution a was 41,100 cps. The polyimide obtained from the polyamic acid solution a has a glass transition temperature of 421 ° C, is non-thermoplastic, and has a thermal expansion coefficient of 10 (ppm / K).

(Synthesis Example 2) Under a nitrogen flow, 17.3 parts by weight of m-TB (0.081 mol parts) and 10.2 parts by weight of TPE-R (0.035 mol parts) were charged into the reaction tank, and the solid content concentration after polymerization was 15 DMAc in an amount of% by weight was dissolved by stirring at room temperature. Next, after adding 25.1 parts by weight of PMDA (0.115 mol parts), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution b. The solution viscosity of the polyamic acid solution b was 38,200 cps. The polyimide obtained from the polyamidic acid solution b has a glass transition temperature of 427 ° C, is non-thermoplastic, and has a thermal expansion coefficient of 22 (ppm / K).

(Synthesis Example 3) Under a nitrogen flow, 16.4 parts by weight of m-TB (0.077 mol parts) and 9.7 parts by weight of TPE-R (0.033 mol parts) were charged into the reaction tank, and the solid content concentration after polymerization was 15 DMAc in an amount of% by weight was dissolved by stirring at room temperature. Next, after adding 16.7 parts by weight of PMDA (0.077 mol parts) and 9.7 parts by weight of BPDA (0.033 mol parts), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution c. The viscosity of the polyamic acid solution c solution was 46,700 cps. The polyimide obtained from the polyamic acid solution c has a glass transition temperature of 366 ° C, is non-thermoplastic, and has a thermal expansion coefficient of 23 (ppm / K).

(Synthesis Example 4) Under a nitrogen flow, 22.4 parts by weight of m-TB (0.105 mol parts) and 4.8 parts by weight of BAPP (0.012 mol parts) were charged into the reaction tank, and the solid content concentration after polymerization became 15% by weight. The amount of DMAc was dissolved by stirring at room temperature. Next, after adding 25.3 parts by weight of PMDA (0.116 mol parts), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution d. The solution viscosity of the polyamic acid solution d was 36,800 cps. The polyimide obtained from the polyamic acid solution d has a glass transition temperature of 408 ° C., is non-thermoplastic, and has a thermal expansion coefficient of 9 (ppm / K).

(Synthesis Example 5) Under a nitrogen flow, 12.3 parts by weight of m-TB (0.058 mol parts), 10.1 parts by weight of TPE-R (0.035 mol parts), and 2.5 parts by weight of p-PDA ( 0.023 mole parts) and DMAc in an amount such that the solid content concentration after polymerization became 15% by weight, was dissolved at room temperature with stirring. Next, after adding 17.5 parts by weight of PMDA (0.080 mol parts) and 10.1 parts by weight of BPDA (0.034 mol parts), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution e. The solution viscosity of the polyamic acid solution e was 42,700 cps. The polyimide obtained from the polyamic acid solution e has a glass transition temperature of 360 ° C, is non-thermoplastic, and has a thermal expansion coefficient of 18 (ppm / K).

(Synthesis Example 6) Under a nitrogen flow, 2.2 parts by weight of m-TB (0.010 mol parts) and 27.6 parts by weight of TPE-R (0.094 mol parts) were charged into the reaction tank, and the solid content concentration after polymerization was 15 DMAc in an amount of% by weight was dissolved by stirring at room temperature. Next, after adding 22.7 parts by weight of PMDA (0.104 mol parts), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution f. The solution viscosity of the polyamic acid solution f was 33,900 cps. The polyimide obtained from the polyamic acid solution f has a glass transition temperature of 446 ° C., a thermoplasticity, and a thermal expansion coefficient of 55 (ppm / K).

(Synthesis Example 7) Under a nitrogen flow, 30.2 parts by weight of BAPP (0.074 mol parts) and DMAc having a solid content concentration of 15% by weight after polymerization were put into a reaction tank, and the solution was stirred and dissolved at room temperature. Next, after adding 22.3 parts by weight of BPDA (0.076 mol parts), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain g of a polyamic acid solution. The solution viscosity of the polyamic acid solution g was 9,800 cps. The polyimide obtained from the polyamidic acid solution g has a glass transition temperature of 252 ° C, a thermoplasticity, and a thermal expansion coefficient of 46 (ppm / K).

(Synthesis Example 8) Under a nitrogen stream, 25.8 parts by weight of TPE-R (0.088 mol parts) and DMAc having a solid content concentration of 15% by weight after polymerization were charged into the reaction tank, and the mixture was stirred at room temperature and added. Dissolve. Next, after adding 26.7 parts by weight of BPDA (0.091 mol parts), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution h. The solution viscosity of the polyamic acid solution h was 8,800 cps. The polyimide obtained from the polyamidic acid solution h has a glass transition temperature of 243 ° C., is thermoplastic, and has a thermal expansion coefficient of 65 (ppm / K).

(Synthesis Example 9) Under a nitrogen flow, 17.6 parts by weight of TPE-R (0.060 mol parts), 1.6 parts by weight of p-PDA (0.015 mol parts), and the solid content concentration after polymerization were 15 DMAc in an amount of% by weight was dissolved by stirring at room temperature. Next, after adding 22.8 parts by weight of BPDA (0.077 mol parts), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution i. The solution viscosity of the polyamic acid solution i was 7,800 cps. The polyimide obtained from the polyamidic acid solution i has a glass transition temperature of 239 ° C., is thermoplastic, and has a thermal expansion coefficient of 65 (ppm / K).

(Synthesis Example 10) Under a nitrogen flow, 11.7 parts by weight of DAPE (0.058 mol parts) and 11.4 parts by weight of TPE-R (0.039 mol parts) were charged, and the solid content concentration after polymerization was 15% by weight. The amount of DMAc was dissolved by stirring at room temperature. Next, after adding 29.5 parts by weight of BPDA (0.100 mol parts), stirring was continued at room temperature for 3 hours to perform a polymerization reaction to obtain a polyamic acid solution j. The solution viscosity of the polyamic acid solution j was 11,200 cps. The polyimide obtained from the polyamidic acid solution j has a glass transition temperature of 265 ° C., is thermoplastic, and has a thermal expansion coefficient of 58 (ppm / K).

[Example 1] The polyamic acid solution prepared in Synthesis Example 7 was uniformly coated on one side of a strip-shaped electrolytic copper foil having a thickness of 12 μm and a width of 1,080 mm so that the thickness after curing became 2.5 μm. After g (first layer), the solvent was removed by heating and drying at 120 ° C. The polyamic acid solution a prepared in Synthesis Example 1 (the second layer) was uniformly applied thereon so that the thickness after curing became 20 μm, and the solvent was removed by heating and drying at 120 ° C. Furthermore, the polyamic acid solution g prepared in Synthesis Example 7 (3rd layer) was uniformly applied so that the thickness after curing became 2.5 μm, and the solvent was removed by heating and drying at 120 ° C. Then, stepwise heat treatment is performed from 130 ° C to 360 ° C to complete the imidization to prepare a single-sided copper-clad laminate.

[Example 2 to Example 8 and Comparative Example 1 to Comparative Example 3] After a polyamic acid resin solution was applied to one surface of an electrolytic copper foil, heat drying and stepwise heat treatment were performed to prepare a single surface coating. In the case of a copper laminated board, a single-sided copper-clad laminated board was obtained in the same manner as in Example 1 except that the resins and thicknesses used in the first to third layers were changed to the structures described in Table 1 below.

Table 1 shows the non-thermoplastic polyimide layer (A) and the thermoplastic polyfluorene in the insulating resin layer of the single-sided copper-clad laminate obtained in Examples 1 to 8 and Comparative Examples 1 to 3. Thickness ratio of imine layer (B) (non-thermoplastic polyimide layer (A) / thermoplastic polyimide layer (B)), in-plane retardation (RO), in-plane retardation in width direction (TD direction) ( RO) deviation (ΔRO) difference between in-plane retardation (ROh) value after heating and in-plane retardation (RO) value before heating (| ROh-RO |), thickness direction of non-thermoplastic polyimide layer Differences in retardation (| ROa-Rob |, | ROv-ROa |, | ROv-ROb |), amount of warpage, and peel strength. In addition, Table 2 shows the in-plane birefringence (Δn) and width direction (Δn) of the insulating resin layer of the single-sided copper-clad laminate obtained in Examples 1 to 8 and Comparative Examples 1 to 3. TD direction) deviation [Δ (Δn)] of the in-plane birefringence (Δn), the difference between the value of the in-plane birefringence (Δnh) after heating and the value of the in-plane birefringence (Δn) before heating (| Δnh-Δn |), and differences in birefringence in the thickness direction of the non-thermoplastic polyimide layer (| Δna-Δnb |, | Δnv-Δna |, | Δnv-Δnb |). Furthermore, Table 3 shows the moisture absorption rate in the insulating resin layer of the single-sided copper-clad laminate obtained in Examples 1 to 4, Example 6, Example 8, and Comparative Examples 1 to 3 ( a _m), moisture absorption (a _m2) after moisture absorption (a _m1) one hour after the humidity and the humidity difference of 2 hours (a _m2 -A _m1).

<IC Wafer Mountability> A dry film was laminated on the surface of the copper foil of the single-sided copper-clad laminate produced in Examples 1 to 8 and Comparative Examples 1 to 3 to resist dry film. After the agent is patterned, a copper foil is etched along the pattern to form a circuit, and a circuit substrate is prepared. At 400 ° C, the IC chip was mounted on the copper wiring side of the obtained circuit board by a bonding process of 0.5 seconds. As a result, for Examples 1 to 8, there was no positional shift between the copper wiring and the IC chip. No adverse conditions occurred. On the other hand, in Comparative Example 1, a positional displacement of the copper wiring and the IC wafer occurred, and in Comparative Examples 2 and 3, a positional displacement of the copper wiring and the IC wafer and warpage of the circuit board occurred, and the mounting was performed. A bad condition occurred in.

[Table 1]

[Table 2]

[table 3]

As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not limited to the said embodiment, It can variously deform.

no

FIG. 1 is a graph showing changes in the moisture absorption rate of resins having different moisture absorption rates and changes in the moisture absorption rate per unit time.

Claims (8)

A metal-clad laminated board includes: an insulating resin layer; and a metal layer laminated on at least one side of the insulating resin layer, the metal-clad laminated board is characterized in that: the insulating resin layer is made of non-thermoplastic polyurethane The amine layer has a thermoplastic polyimide layer containing a thermoplastic polyimide on at least one side, and the insulating resin layer satisfies the following conditions (i) and (ii): (i) in-plane birefringence ( The value of Δn) is 2 × 10 ^-3 or less; (ii) The deviation [Δ (Δn)] of the in-plane birefringence (Δn) in the width direction (lateral direction) is 4 × 10 ^-4 or less; The conditions (iii), or both (iv) and (v), or both (vi) and (vii): (iii) In-plane birefringence (Δnh) after heating at 250 ° C for 30 minutes The difference (Δnh-Δn) between the value of) and the value of the in-plane birefringence (Δn) before heating is ± 2 × 10 ^-4 or less; (iv) in the thickness direction of the non-thermoplastic polyimide layer , The birefringence (Δna) at a point of 1.5 μm in the direction of the central portion with one surface as the base point, and the other with the other The difference (Δna-Δnb) of the birefringence (Δnb) at a point of 1.5 μm in the direction of the central portion of the base point is ± 0.01 or less; (v) the central portion in the thickness direction with the Δna and the Δnb The difference in the average value (Δnv) of the total (Δna + Δnb + Δnc) of the birefringence (Δnc) in the sample is ± 0.01 or less in any of the Δna and Δnb; (vi) dried at 80 ° C. 1 After an hour, at a constant temperature and constant humidity of 23 ° C and 50% relative humidity, the moisture absorption (A _m ) after humidity adjustment for 4 hours is 1.0% by weight or less; (vii) After drying at 80 ° C for 1 hour, at 23 ° C , 50% relative humidity, temperature and humidity, moisture absorptivity difference (a _m1) one hour after the humidity and moisture absorption (a _m2) in the same conditions after its humidity for 2 hours (a _m2 -A _m1) It is 0.2% by weight or less. The metal-clad laminate according to item 1 of the scope of the patent application, wherein the non-thermoplastic polyimide contains a tetracarboxylic acid residue and a diamine residue, and is 100 mol parts relative to all the diamine residues. The diamine residue derived from the diamine compound represented by the following general formula (1) is 20 mol parts or more, [In the general formula (1), the linking group Z represents a single bond or -COO-, and Y independently represents a monovalent hydrocarbon having 1 to 3 carbon atoms or an alkoxy having 1 to 3 carbon atoms which may be substituted with a halogen atom or a phenyl group. Group, or perfluoroalkyl group or alkenyl group having 1 to 3 carbon atoms, n represents an integer of 0 to 2, and p and q independently represent an integer of 0 to 4]. The metal-clad laminate according to item 2 of the scope of the patent application, wherein 100 mole parts of all diamine residues contained in the non-thermoplastic polyimide is represented by the general formula (1) The diamine residue derived from the diamine compound is in the range of 70 mol parts to 95 mol parts, and the total amount of the diamine residues selected from the following general formula (2) and general formula (3) is In the range of 5 moles to 30 moles, [In the general formula (2) and the general formula (3), R ₅ , R ₆ , R _7, and R ₈ each independently represent a halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms which may be substituted with a halogen atom. Or alkenyl, X independently represents a group selected from -O-, -S-, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CO-, -COO-, Divalent group in -SO _2- , -NH- or -NHCO-, X ₁ and X ₂ each independently represent a single bond, and are selected from -O-, -S-, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CO-, -COO-, -SO _2- , -NH- or -NHCO-, but both X ₁ and X ₂ are single bonds Except for the case where m, n, o, and p independently represent integers from 0 to 4]. The metal-clad laminate according to item 2 of the scope of the patent application, wherein the thermoplastic polyimide comprises a tetracarboxylic acid residue and a diamine residue, and is 100 mol parts relative to all the diamine residues, and is selected from The total amount of diamine residues in the following general formula (2) and general formula (3) is 50 mol parts or more, [In the general formula (2) and the general formula (3), R ₅ , R ₆ , R _7, and R ₈ each independently represent a halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms which may be substituted with a halogen atom. Or alkenyl, X independently represents a group selected from -O-, -S-, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CO-, -COO-, Divalent group in -SO _2- , -NH- or -NHCO-, X ₁ and X ₂ each independently represent a single bond, and are selected from -O-, -S-, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CO-, -COO-, -SO _2- , -NH- or -NHCO-, but both X ₁ and X ₂ are single bonds Except for the case where m, n, o, and p independently represent integers from 0 to 4]. The metal-clad laminate according to item 3 or item 4 of the scope of patent application, wherein the diamine residue represented by the general formula (2) is 1,3-bis (4-aminophenoxy) benzene The derived diamine residue, and the diamine residue represented by the general formula (3) is a diamine derived from 2,2-bis [4- (4-aminophenoxy) phenyl] propane Residues. The metal-clad laminate according to any one of claims 1 to 4, wherein the thickness (A) of the non-thermoplastic polyimide layer and the thickness of the thermoplastic polyimide layer The thickness ratio (A) / (B) of (B) is in the range of 1 to 20. The metal-clad laminate according to any one of claims 1 to 4, wherein the length in the width direction (lateral direction) is 490 mm or more. A circuit board is characterized in that the metal layer of the metal-clad laminated board according to any one of claims 1 to 7 of the scope of patent application is processed into wiring.